Synthesis and photophysical properties of polyethylene containing pyrenyl units in the side chain

Naofumi Naga, Nobuo Tano, Haruhiko Tomoda

研究成果: Article

抄録

Copolymerization of ethylene and diallyl-bis(pyren-1-yl)-silane (APyS) was investigated with zirconocene catalysts, rac-ethylenebis(indenyl)zirconium dichloride (1) and diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (2), using methylaluminoxane as a cocatalyst. APyS was copolymerized via both 1,2-insertion and cyclization insertion, and cyclization selectivity, ratio of cyclized insertion unit, of APyS in the copolymers obtained with Catalyst 1 was higher than that obtained with Catalyst 2. Catalyst 2 showed a higher reactivity for APyS than Catalyst 1. Photophysical properties of the copolymer were investigated by UV-vis and photoluminescence (PL) spectroscopy, and absorption and fluorescence derived from pyrenyl groups were detected in the copolymers. Chloroform solution of the copolymer showed emission derived from both monomer and eximer of pyrenyl units. Only the emission derived from eximer of pyrenyl units was observed in the cast film. The polarized PL spectrum of an oriented film showed anisotropy, and the polarization excitation parallel to the drawing direction showed high fluorescence intensity.

元の言語English
ページ(範囲)4223-4229
ページ数7
ジャーナルJournal of Polymer Science, Part A: Polymer Chemistry
50
発行部数20
DOI
出版物ステータスPublished - 2012 10 15

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Polyethylene
Polyethylenes
Copolymers
Catalysts
Cyclization
Zirconium
Fluorescence
Silanes
Photoluminescence spectroscopy
Chloroform
Chlorine compounds
Ultraviolet spectroscopy
Copolymerization
Photoluminescence
Ethylene
Anisotropy
Monomers
Polarization

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

これを引用

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title = "Synthesis and photophysical properties of polyethylene containing pyrenyl units in the side chain",
abstract = "Copolymerization of ethylene and diallyl-bis(pyren-1-yl)-silane (APyS) was investigated with zirconocene catalysts, rac-ethylenebis(indenyl)zirconium dichloride (1) and diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (2), using methylaluminoxane as a cocatalyst. APyS was copolymerized via both 1,2-insertion and cyclization insertion, and cyclization selectivity, ratio of cyclized insertion unit, of APyS in the copolymers obtained with Catalyst 1 was higher than that obtained with Catalyst 2. Catalyst 2 showed a higher reactivity for APyS than Catalyst 1. Photophysical properties of the copolymer were investigated by UV-vis and photoluminescence (PL) spectroscopy, and absorption and fluorescence derived from pyrenyl groups were detected in the copolymers. Chloroform solution of the copolymer showed emission derived from both monomer and eximer of pyrenyl units. Only the emission derived from eximer of pyrenyl units was observed in the cast film. The polarized PL spectrum of an oriented film showed anisotropy, and the polarization excitation parallel to the drawing direction showed high fluorescence intensity.",
keywords = "copolymerization, ethylene, fluorescence, functionalization of polymers, metallocene catalysts, optical property, polyethylene, pyrene, Ziegler-Natta polymerization, zirconocene",
author = "Naofumi Naga and Nobuo Tano and Haruhiko Tomoda",
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AU - Naga, Naofumi

AU - Tano, Nobuo

AU - Tomoda, Haruhiko

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N2 - Copolymerization of ethylene and diallyl-bis(pyren-1-yl)-silane (APyS) was investigated with zirconocene catalysts, rac-ethylenebis(indenyl)zirconium dichloride (1) and diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (2), using methylaluminoxane as a cocatalyst. APyS was copolymerized via both 1,2-insertion and cyclization insertion, and cyclization selectivity, ratio of cyclized insertion unit, of APyS in the copolymers obtained with Catalyst 1 was higher than that obtained with Catalyst 2. Catalyst 2 showed a higher reactivity for APyS than Catalyst 1. Photophysical properties of the copolymer were investigated by UV-vis and photoluminescence (PL) spectroscopy, and absorption and fluorescence derived from pyrenyl groups were detected in the copolymers. Chloroform solution of the copolymer showed emission derived from both monomer and eximer of pyrenyl units. Only the emission derived from eximer of pyrenyl units was observed in the cast film. The polarized PL spectrum of an oriented film showed anisotropy, and the polarization excitation parallel to the drawing direction showed high fluorescence intensity.

AB - Copolymerization of ethylene and diallyl-bis(pyren-1-yl)-silane (APyS) was investigated with zirconocene catalysts, rac-ethylenebis(indenyl)zirconium dichloride (1) and diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (2), using methylaluminoxane as a cocatalyst. APyS was copolymerized via both 1,2-insertion and cyclization insertion, and cyclization selectivity, ratio of cyclized insertion unit, of APyS in the copolymers obtained with Catalyst 1 was higher than that obtained with Catalyst 2. Catalyst 2 showed a higher reactivity for APyS than Catalyst 1. Photophysical properties of the copolymer were investigated by UV-vis and photoluminescence (PL) spectroscopy, and absorption and fluorescence derived from pyrenyl groups were detected in the copolymers. Chloroform solution of the copolymer showed emission derived from both monomer and eximer of pyrenyl units. Only the emission derived from eximer of pyrenyl units was observed in the cast film. The polarized PL spectrum of an oriented film showed anisotropy, and the polarization excitation parallel to the drawing direction showed high fluorescence intensity.

KW - copolymerization

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KW - fluorescence

KW - functionalization of polymers

KW - metallocene catalysts

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KW - polyethylene

KW - pyrene

KW - Ziegler-Natta polymerization

KW - zirconocene

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